Bachelorette's Chris Harrison 'Believed Brad and Emily Would Work'

When a couple get engaged on The Bachelor or The Bachelorette, "I get caught up in the moment just like our viewers do," host Chris Harrison tells PEOPLE.

But when a couple part ways, like Bachelor Brad Womack and his fiancée, Emily Maynard, recently did – well, that's a different story.

"I believed Brad and Emily would work," says Harrison, whose one-on-one chat with Maynard will air during The Bachelorette Monday, 8 p.m. on ABC. "I knew the interview was going to be very difficult for her and for me."

From the moment her car pulled up in front of the Bachelor mansion, the single mom from Charlotte, N.C., couldn't conceal her heartbreak, Harrison says.

"She saw the house and she saw me, and from there on it was really an emotional roller coaster for her. It was tough for her to be back in that house where it all started," he says.

"She thought she'd be planning a wedding or even be married to Brad. She told me in the interview, 'I never thought I would be this girl coming on this show saying why we broke up and why it couldn't work.' "

Harrison says that if Maynard had her way, she never would have appeared on camera to confirm the split.

"I want people to know she was very reluctant to come on," Harrison says. "Because of all of the media attention, all the tabloids, all the paparazzi and this insatiable appetite for information on the relationship, she kind of bit the bullet and was the one to step forward and it was incredibly brave of her to speak up all by herself."

He added, "In a way, it wasn't an interview, but this was her saying it out loud for the first time and making it real."